Mesoporous　organosilica　membranes　were　synthesized　by　sol-gel　and　dip-coating　method　using　1,2-bis　(triethoxysilyl)　ethane　(BTESE)　as　precursor,　triblock　copolymer　poly　(ethylene　oxide)-block-poly　(propylene　oxide)　block-poly　(ethylene　oxide)　(P123)　as　surfactant　template.　After　silylated　with　1H,1H,2H,2H-perfluorooctyltriethoxysilane　(PFOTES,C8)　by　post-grafting　approach,　the　membranes　were　used　for　the　separation　of　hazardous　volatile　organic　compounds　(VOCs)　from　water　via　pervaporation　process.　The　results　show　that　ethanol-extraction　is　considerably　effective　to　remove　the　surfactant　template.　The　membranes　show　a　smooth　surface　and　a　sharp　pore　size　distribution　centered　at　3.5　nm.　The　hydrophobic　property　has　been　enhanced　after　silylated　with　PFOTES,　leading　to　a　water　contact　angle　of　(105　+/-　0.11)degrees.　Hydrophobic　mesoporous　organosilica　membranes　are　selective　toward　VOCs　and　show　the　highest　total　flux　of　0.36　kgm(-2)h(-1)　for　methyl　tert-butyl　ether　(MTBE)　aqueous　solution　and　the　highest　MTBE/water　separation　factor　of　27.9.　The　pervaporation　performance　depends　on　the　affinity　between　VOCs　and　grafted　C8　groups.　Repeated　separation　experiments　reveal　that　the　membranes　are　durable　in　aqueous　solution　due　to　the　presence　of　water-resistant　Si-C　bonds　within　the　framework.